CN110389117A - Recessed soil-thiocoumarin function hybrid material and its preparation method and application - Google Patents
Recessed soil-thiocoumarin function hybrid material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses recessed soil-thiocoumarin function hybrid materials, which is characterized in that it is the thiocoumarin fluorescent dye to be matched by molecular dimension and recessed native duct size, and hydridization is prepared under certain condition with recessed soil；Its fluorescence reaction that specific selectivity can occur with mercury ion, so that the fluorescence intensity under a certain wavelength is promoted significantly.The distinguishable color reaction of naked eyes can occurs in it simultaneously, it is thus possible in the detection of mercury ion, and then detect the mercury pollution of water body.The invention also discloses recessed soil-thiocoumarin function hybrid material preparation methods, step includes recessed native pre-treatment step and wet process hybridisation step, recessed native specific surface area after treatment is highly improved, isopropanol wet process hydridization can effectively facilitate the dissociation of recessed soil and the further combination of promotion and dyestuff, and high temperature bakes the hydridization for making to promote thiocoumarin and recessed soil while recessed soil dehydration.
Description
Technical field
The invention belongs to heavy metal analysis technical field, it is related to the phosphor for water body or mercury in soils ion detection
Material, in particular to recessed soil-thiocoumarin function hybrid material and its preparation method and application.
Background technique
The main source of the pollution of heavy metal is industrial pollution, secondly from traffic pollution and living garbage pollution.Work
Industry heavy metal pollution passes through " three wastes " mostly and is discharged into environment, and persistence presence in the environment of accumulating over a long period.Heavy metal pollution
Type has very much, Cd2+、Hg2+、Pb2+It is its chief component.Currently, these three food-safe great heavy metals of influence
Ion has seriously affected the export abroad of China's food.Wherein, the harm of mercury pollution is particularly acute.
Mercury is often referred to as mercury, and toxicity is bigger after mercury and mercuric compounds belong to extremely toxic substance, especially mercury methylation.
It is mercurous few in natural water, it is usually no more than 0.1 μ g/L.Mercury in normal human blood is less than 5-10 μ g/L, and the mercury in urine is dense
Degree is less than 20 μ g/L.Mercury can accumulate in human body and final life threatening health.Mercury and mercuric compounds they be mainly used for battery
Manufacture, precious metal smelting, catalyst, illuminator lamp, drug, pigment and scientific measurement instrument etc..Mercury metal in blood enters
After brain tissue, it can gradually accumulate in brain tissue, will cause serious harm to brain tissue when reaching a certain amount, main table
It is now neurological symptom.And another part mercury will be transferred to kidney, cause kidney failure.If acute mercury poisoning can lure
Send out hepatitis and blood urine.And mercury poisoning be mostly it is chronic, take a long time just show.Once the water body that mercury has occurred is dirty
Dye, it is extremely difficult to administer, be difficult to eliminate its influence after many years.Once sensational minamata disease is exactly mercury slow poisoning
A kind of performance.
Since heavy metal ion is played an extremely important role in life science, medicine and environmental science, and work
Industry field largely uses heavy metal ion again, and heavy metal ion pollution is caused to be on the rise.Therefore, a kind of pair of heavy metal is developed
The method that ion is measured in real time is extremely important.
And fluorescent technique is very sensitive, because it is substantially a kind of zero background technique.It is glimmering with the development of fluorescent technique
Light probe is rapidly developed.Fluorescence probe is a kind of fluorescence molecule, it ultraviolet to there is characteristic fluorescence between near infrared region,
And its photoluminescent property such as excites and launch wavelength, intensity, polarization and service life can be with refractive index, the viscosity etc. of locating environment
The change of property and delicately change.Fluorescopy probe in detecting heavy metal is with highly sensitive, accuracy and good selection
Property is widely applied.It is known as chemiluminescence sensor using the chemical sensor of change in fluorescence.Chemical molecular fluorescence sense
Device or probe can be reversible and selectively combine specific molecular system, and pass through oxidation-reduction potential, UV absorption or glimmering
The variation of optical emission spectroscopy etc. detects to realize.It has many advantages, such as easy to operate, low in cost and high sensitivity, thus in life
Life science, environmental science and clinical medicine etc. have been widely used.
Because coumarin derivatives have a good fluorescence property, and cumarin parent fluorescence quantum yield it is high,
Stokes is displaced big, good light stability and toxicity is lower, so many researchers are cured the exploitation of Coumarins fluorescence probe
It pays attention in.Coumarin fluorescent probe includes monoamine oxidase, beta-lactam enzyme gene, hydroperoxide kind, CN ionic species etc., mesh
Before, currently, there is also many defects at present based on the fluorescence probe based on fluorescent dye, and such as: stability is poor, is difficult to back
It receives and utilizes, mostly detects to easily lead to secondary pollution etc. in organic phase.
Summary of the invention
In view of the drawbacks of the prior art, the present invention provides recessed soil-thiocoumarin function hybrid materials, can be with mercury
The fluorescence reaction of specific selectivity occurs for ion, so that the fluorescence intensity under a certain wavelength is promoted significantly.It can occur simultaneously
Visually distinguishable color reaction, it is thus possible in the detection of mercury ion, and then detect the mercury pollution of water body.Of the invention is another
One is designed to provide recessed soil-thiocoumarin function hybrid material preparation method and application, and preparation method is simple to operation,
Hybrid material good water solubility obtained, stability is high, is suitable for use in the detection of Mercury in Water Body ion.
The present invention is achieved by the following technical solutions:
Recessed soil-thiocoumarin function hybrid material is the thio tonka-bean to be matched by molecular dimension and recessed native duct size
Plain fluorescent dye, hydridization is prepared under certain condition with recessed soil；
The structural formula of the thiocoumarin are as follows:
。
The thiocoumarin is to be reacted to be prepared with lawesson reagent by coumarin 6, and preparation route is as follows:
Further improvement of the present invention scheme are as follows:
Recessed soil-thiocoumarin function hybrid material preparation method, includes the following steps:
Recessed soil pretreatment:
Raw ore is rolled, grinds recessed soil after crossing 200 meshes, is ground 5 ~ 10 minutes, be added in recessed soil deionized water mashing, from
The non-clay impurity of lower layer is removed after the heart, mashing and centrifugally operated 3 ~ 4 times in repetitions；By gained paste body shape after above-mentioned mashing and centrifugation
Recessed soil is put into refrigerator freezing 6 ~ 7 hours, takes out and thaws, and the recessed earth sample twin rollers after defrosting squeeze roller 5 ~ 6 times, scrape
To the sample after roller and isopropanol solvent displacement is carried out, obtains pretreated recessed soil；
Wet process hydridization:
It takes pretreated recessed soil to mix with thiocoumarin dyestuff, isopropanol is added, high speed is beaten, and is configured to slurry, is stirred
Afterwards；Above-mentioned slurry is placed in ultrasonic wave after shaking, is dried in drying box, takes out grinding, then be placed in a vacuum drying oven height
Temperature bakes；Sample after baking is eluted loose thiocoumarin postposition with solvent to dry in a vacuum drying oven, is obtained recessed
Soil-thiocoumarin function hybrid material after vacuumizing, is passed through inert gas preservation.
Further, the isopropanol solvent displacement step are as follows: by isopropanol, high speed is beaten to the sample dispersion after roller
Supernatant is abandoned after slurry, high speed centrifugation and obtains lotion, is repeated isopropanol solvent and is replaced 2 ~ 3 times, obtains pretreated recessed soil；It is described to beat
Slurry speed is 8000 ~ 12000 rpm, and beating time is 10 ~ 30min；Centrifugal speed is 2500 ~ 3500 rpm, and centrifugation time is
20~40min。
Further, in the recessed native pre-treatment step, beating rate is 8000 ~ 12000 rpm, beating time is 20 ~
40min；Centrifugal speed is 3000 ~ 4000 rpm, and centrifugation time is 20 ~ 40min.
Further, in the wet process hybridisation step, the mass ratio of pretreated recessed soil and thiocoumarin dyestuff is
20~30:1。
Further, the solid content of slurry is 1 ~ 3wt% in the wet process hybridisation step.
Further, drying temperature is 60 DEG C ~ 80 DEG C in the wet process hybridisation step, and drying time is 4 ~ 6h；Bake temperature
Degree is 100 DEG C ~ 140 DEG C, and baking time is 40 ~ 60h.
Further, the step of solvent elutes in the wet process hybridisation step are as follows: the sample after baking is placed in solvent,
High speed centrifugation, after centrifugation take out upper layer liquids recovery, lower sediment thing it is dry recessed soil-thiocoumarin function hydridization
Material；The centrifugal rotational speed be 6000 ~ 10000 rpm, centrifugation time be 20 ~ 40min, the drying in a vacuum drying oven into
Row, drying temperature are 20 ~ 40 DEG C, and drying time is 8 ~ 14h.
Further, eluting solvent is methylene chloride or isopropanol or both mixing in the wet process hybridisation step.
Further improvement project of the invention are as follows:
The application of recessed soil-thiocoumarin function hybrid material, the function hybrid material are used for the detection of mercury ion.
The invention has the benefit that
The thiocoumarin fluorescent dye that the present invention selects a kind of molecular dimension and recessed native duct size to match, then by recessed
Soil and dyestuff hydridization under certain condition, prepare high stability can organic and inorganic functionality hydridization dyestuff, examined with this
Survey mercury pollution.The hydridization dyestuff can not only highly sensitive, highly selective identification Hg2+Ion, additionally it is possible to solve traditional some
The defect of fluorescence probe based on fluorescent dye.The hybrid inorganic-organic dyestuff can be detected in water phase, and be stablized
Property is greatly improved compared with pure dye, can be good at saving.
The thiocoumarin that the present invention selects is synthesized from coumarin 6, and special choosing can occurs in it with mercury ion
The fluorescence reaction of selecting property, so that the fluorescence intensity under a certain wavelength is promoted significantly.The distinguishable color of naked eyes can occurs in it simultaneously
Reaction, is changed into the green after reacting with mercury ion from the red of cumarin script, it is thus possible in the detection of mercury ion,
And then detect the mercury pollution of water body.
The recessed soil that the present invention uses is internal containing nanoscale duct extremely abundant, so possessing king-sized interior specific surface
Product, and since recessed native crystal habit is small, surface texture is complicated, therefore recessed soil also has biggish external surface area, recessed soil
With unique groove cellular structure, thiocoumarin molecule is in directrix plane structure and the groove duct structure size phase with recessed soil
Matching, therefore the two can form good molecular matching effect.
In the present invention, recessed native specific surface area after treatment is highly improved, and the specific surface of hybrid material is compared with original soil
There is very big reduction, illustrate that hydridization is all right, and also has the presence of a large amount of dyestuffs in the cellular structure of recessed soil；By methylene chloride
After elution, less, hydridization dyestuff still has very high hydridization rate for specific surface area variation, illustrates that hybrid material stability is preferable,
With certain anti-solvent elution property.
Detailed description of the invention
Fig. 1 is the infrared absorpting light spectra of embodiment 4；
Fig. 2 is the color change figure of liquid in 11 reagent bottles when embodiment 5 stands 5min, 30min, 1h, 5h；
Fig. 3 is the color change figure of liquid in 11 reagent bottles when embodiment 6 stands 5min, 30min, 1h, 5h；
Fig. 4 is the ultraviolet-visible spectrogram of embodiment 7；
Wherein, a- thiocoumarin, b-Hg2++ thiocoumarin, the recessed soil of c--thiocoumarin function hybrid material, d-Hg2+
+ recessed soil-thiocoumarin function hybrid material.
Specific embodiment
Embodiment 1
One, the synthesis of thiocoumarin
Coumarin 6 (0.35 g, 1.0 mmol) and lawesson reagent (0.81 g, 2.0 mmol) are separately added into two mouth flask,
Then it is added in flask in 15 ml dry toluenes and forms mixture.It is put into rotor in flask and flask is placed in constant temperature and adds
In pyromagnetic force blender.Cooling water circulating device is built, mixture is heated to 120 DEG C, and sustained response under nitrogen protection
1 day.It is cooled to room temperature after the reaction was completed.
Reaction product is extracted with methylene chloride and water, and with passing through column layer analysis (solvent ratio PE:DCM=1:2 ~ 1:3)
Products therefrom is purified to get the thio derivative (0.23 g, 62%) of the cumarin is arrived.High resolution mass spectrum is as follows:1H NMR
(300 MHz, CDCl3) δ 8.96 (br d, J = 0.6 Hz, 1H), 8.01 (d, J = 8.1 Hz, 1H),
7.95(d, J = 7.8 Hz, 1H), 7.53 (d, J = 9.0 Hz, 1H), 7.48 (ddd, J = 7.7 Hz, 7.6
Hz and 1.4 Hz,1H), 7.37 (ddd, J = 7.6 Hz, 7.6 Hz, and 1.1 Hz, 1H), 6.73 (dd,J = 9.0 Hz and 2.4 Hz,1H), 6.67 (d, J = 1.8 Hz, 1H), 3.45 (q, J = 7.1 Hz,
4H), 1.25 (t, J = 7.2 Hz, 6H); 13C NMR (75 MHz, CDCl3) δ 192.80, 164.40,
160.04, 153.07, 151.55, 139.03, 136.37, 131.38, 126.23, 124.84, 122.14,
121.64, 111.90, 111.37, 96.39, 45.52, 12.66; HRMS (DIP); m/z calcd for
C20H18N2OS2[M]+: 366.0861, found 366.0857. show that synthesized product is required thio by the mass spectrum
Cumarin.
Two, recessed soil-thiocoumarin function hybrid material preparation
Recessed soil pretreatment:
Raw ore is rolled, recessed soil is ground after crossing 200 meshes, grinds 5 ~ 10min, deionized water mashing, centrifugation are added in recessed soil
The non-clay impurity of lower layer is removed afterwards, and beating rate is 10000 rpm, beating time 30min；Centrifugal speed is 3500 rpm,
Centrifugation time is 300min, is beaten in repetition and centrifugally operated 3 ~ 4 times；The gained recessed soil of paste body shape after above-mentioned mashing and centrifugation is put
Enter refrigerator freezing 6 ~ 7 hours, take out and thaw, the recessed earth sample twin rollers after defrosting squeeze roller 5 ~ 6 times, scrape to after roller
Sample and carry out isopropanol solvent displacement, obtain pretreated recessed soil；
The isopropanol solvent displacement step are as follows: by isopropanol, high speed is beaten, after high speed centrifugation to the sample dispersion after roller
It abandons supernatant and obtains lotion, repeat isopropanol solvent and replace 2 ~ 3 times, obtain pretreated recessed soil；The beating rate is 10000
Rpm, beating time 20min；Centrifugal speed is 3000 rpm, centrifugation time 30min.
Wet process hydridization:
Taking mass ratio is that the pretreated recessed soil of 25:1 is mixed with thiocoumarin dyestuff, and isopropanol is added, and high speed is beaten, configuration
The slurry for being 2wt% at solid content, after stirring；Above-mentioned slurry is placed in ultrasonic wave after shaking 15min, is dried in drying box
Dry, drying temperature is 70 DEG C, drying time 5h, takes out grinding, then is placed in a vacuum drying oven high temperature baking, and stoving temperature is
120 DEG C, baking time 48h；Sample after baking is eluted into loose thiocoumarin with solvent and is placed on vacuum drying
It is dry in case, recessed soil-thiocoumarin function hybrid material is obtained, after vacuumizing, is passed through inert gas preservation.
The step of solvent elutes are as follows: the sample after baking is placed in methylene chloride, high speed centrifugation, after centrifugation
Take out upper layer liquids recovery, lower sediment thing it is dry recessed soil-thiocoumarin function hybrid material；The centrifugal rotational speed is
8000 rpm, centrifugation time 30min, the drying carry out in a vacuum drying oven, and drying temperature is 30 DEG C, and drying time is
12h。
Embodiment 2: recessed soil-thiocoumarin function hybrid material preparation
Recessed soil pretreatment:
Raw ore is rolled, recessed soil is ground after crossing 200 meshes, grinds 5 ~ 10min, deionized water mashing, centrifugation are added in recessed soil
The non-clay impurity of lower layer, beating rate 8000rpm, beating time 40min are removed afterwards；Centrifugal speed is 3000rpm, centrifugation
Time is 40min, is beaten in repetition and centrifugally operated 3 ~ 4 times；The gained recessed soil of paste body shape after above-mentioned mashing and centrifugation is put into ice
Case freezes 6 ~ 7 hours, takes out and thaws, and the recessed earth sample twin rollers after defrosting squeeze roller 5 ~ 6 times, scrape to the sample after roller
Product simultaneously carry out isopropanol solvent displacement, obtain pretreated recessed soil；
The isopropanol solvent displacement step are as follows: by isopropanol, high speed is beaten, after high speed centrifugation to the sample dispersion after roller
It abandons supernatant and obtains lotion, repeat isopropanol solvent and replace 2 ~ 3 times, obtain pretreated recessed soil；The beating rate is 12000
Rpm, beating time 10min；Centrifugal speed is 2500 rpm, centrifugation time 40min.
Wet process hydridization:
Taking mass ratio is that the pretreated recessed soil of 20:1 is mixed with thiocoumarin dyestuff, and isopropanol is added, and high speed is beaten, configuration
The slurry for being 1wt% at solid content, after stirring；Above-mentioned slurry is placed in ultrasonic wave after shaking 15min, is dried in drying box
Dry, drying temperature is 60 DEG C, drying time 6h, takes out grinding, then is placed in a vacuum drying oven high temperature baking, and stoving temperature is
100 DEG C, baking time 60h；Sample after baking is eluted into loose thiocoumarin with solvent and is placed on vacuum drying
It is dry in case, recessed soil-thiocoumarin function hybrid material is obtained, after vacuumizing, is passed through inert gas preservation.
The step of solvent elutes are as follows: the sample after baking is placed in methylene chloride, high speed centrifugation, after centrifugation
Take out upper layer liquids recovery, lower sediment thing it is dry recessed soil-thiocoumarin function hybrid material；The centrifugal rotational speed is
6000 rpm, centrifugation time 40min, the drying carry out in a vacuum drying oven, and drying temperature is 20 DEG C, and drying time is
14h。
Embodiment 3: recessed soil-thiocoumarin function hybrid material preparation
Recessed soil pretreatment:
Raw ore is rolled, recessed soil is ground after crossing 200 meshes, grinds 5 ~ 10min, deionized water mashing, centrifugation are added in recessed soil
The non-clay impurity of lower layer is removed afterwards, and beating rate is 12000 rpm, beating time 20min；Centrifugal speed is 4000 rpm,
Centrifugation time is 20min, is beaten in repetition and centrifugally operated 3 ~ 4 times；The gained recessed soil of paste body shape after above-mentioned mashing and centrifugation is put
Enter refrigerator freezing 6 ~ 7 hours, take out and thaw, the recessed earth sample twin rollers after defrosting squeeze roller 5 ~ 6 times, scrape to after roller
Sample and carry out isopropanol solvent displacement, obtain pretreated recessed soil；
The isopropanol solvent displacement step are as follows: by isopropanol, high speed is beaten, after high speed centrifugation to the sample dispersion after roller
It abandons supernatant and obtains lotion, repeat isopropanol solvent and replace 2 ~ 3 times, obtain pretreated recessed soil；The beating rate is 8000
Rpm, beating time 30min；Centrifugal speed is 3500 rpm, centrifugation time 20min.
Wet process hydridization:
Taking mass ratio is that the pretreated recessed soil of 30:1 is mixed with thiocoumarin dyestuff, and isopropanol is added, and high speed is beaten, configuration
The slurry for being 3wt% at solid content, after stirring；Above-mentioned slurry is placed in ultrasonic wave after shaking 15min, is dried in drying box
Dry, drying temperature is 80 DEG C, drying time 4h, takes out grinding, then is placed in a vacuum drying oven high temperature baking, and stoving temperature is
140 DEG C, baking time 40h；Sample after baking is eluted into loose thiocoumarin with solvent and is placed on vacuum drying
It is dry in case, recessed soil-thiocoumarin function hybrid material is obtained, after vacuumizing, is passed through inert gas preservation.
The step of solvent elutes are as follows: the sample after baking is placed in methylene chloride, high speed centrifugation, after centrifugation
Take out upper layer liquids recovery, lower sediment thing it is dry recessed soil-thiocoumarin function hybrid material；The centrifugal rotational speed is
10000 rpm, centrifugation time 20min, the drying carry out in a vacuum drying oven, and drying temperature is 40 DEG C, drying time
For 8h.
Embodiment 4: recessed soil-thiocoumarin function hybrid material characterization test
1, infrared detection
Using the 5700 type Fourier infrared spectrograph of Nicolet of Sai Mofei company, U.S. production to recessed made from embodiment 1
Soil-thiocoumarin function hybrid material is detected.Detecting temperature is 17 DEG C, and detection method is KBr pressed disc method.Pass through detection
And it is as shown in Figure 1 to handle the infrared absorpting light spectra obtained after data.
As can be drawn from Figure 1, the dyestuff as made from hydridization maintains the recessed original characteristic peak of soil.Attapulgite (A) In
3417 cm-1With 3253 cm-1Absorption peak is derived from the stretching vibration of zeolite water-OH, 1657 cm-1The absorption peak at place is adsorption
The bending vibration of water H-O-H, 1031 cm-1The absorption peak at place is the stretching vibration due to Si-O-Si key, 985 cm-1Place be by
In the bending vibration of Si-OH.Meanwhile the characteristic peak of dyestuff is also shown in hybrid material, and such as: in 2969 cm-1It inhales at place
Peak is received derived from the flexible vibration of C-H on ethyl, 756 cm-1For absorption peak outside the face of C-H on monosubstituted phenyl ring etc..It is possible thereby to judge
Dyestuff and the recessed not simple Material cladding of soil out form hybrid and have both certain characteristics of the two.
2, specific surface is tested
It is detected using II 3020 specific surface area of TriStar and pore-size distribution analyzer of Merck & Co., Inc, U.S. production.
Test sample is respectively the hybrid material in embodiment 1 before pretreated recessed soil, elution, the hydridization material after elution
Material.Through detecting, the specific surface area (BET Surface Area) of recessed soil is 92.4107 m2/ g, the ratio of the hybrid material before elution
Surface area (BET Surface Area) is 52.5189 m2/ g, hybrid material specific surface area (the BET Surface after elution
It Area) is 65.3416 m2/g。
Obtained by the above testing result: recessed native specific surface area after treatment is highly improved；Hybrid material
Specific surface has very big reduction compared with original soil, illustrates that hydridization is all right, and also has the presence of a large amount of dyestuffs in the cellular structure of recessed soil；
After dichloromethane eluent, less, hydridization dyestuff still has very high hydridization rate, illustrates hybrid material for specific surface area variation
Stability is preferable, with certain anti-solvent elution property.
Recessed soil-thiocoumarin function hybrid material is used for Hg2+Detection test
The configuration of recessed soil-thiocoumarin function hybrid material solution: quantitative concentrations are 1 × 10 in the volumetric flask of 100 mL-4
The recessed soil of mol/L-thiocoumarin function hybrid material aqueous solution；
The configuration of solion: respectively at quantitative concentrations in the volumetric flask of 10 10 mL be 1 × 10-3The Cd of mol/L2+、Pb2+、
Mg2+, Fe3+、Ca2+、Zn2+、Na+、Li+、Cu2+、Co2+、Hg2+Solion.
Embodiment 5: recessed soil-response test of the thiocoumarin function hybrid material for different ions
The 1 × 10 of 5mL is separately added into the reagent bottle of 11 10 mL with cover-4 Recessed soil-thiocoumarin function of mol/L
Hybrid material aqueous solution is separately added into the 1 × 10 of 2mL in 10 reagent bottles thereto-3The Cd of mol/L2+、Pb2+、Mg2+, Fe3 +、Ca2+、Zn2+、Na+、Li+、Cu2+、Co2+Solion, cover tightly bottle cap, stood after concussion, observation stand 5min, 30min,
When 1h, 5h in 11 reagent bottles liquid color, photograph to record, as shown in Figure 2.
As can be seen from Figure 2, common metal ion can not make recessed soil matrix thiocoumarin dyestuff that obvious discoloration, packet occur
Include some close sulfur metal ions.Illustrate that common metal ion cannot generally cause macroscopic discoloration, these ions not shadow
The effect of naked eye is rung, therefore can directly observe very much in solution whether contain Hg2+。
Embodiment 6: Hg of the recessed soil-thiocoumarin function hybrid material for various concentration2+Response test
The 1 × 10 of 5mL is separately added into the reagent bottle of 11 10 mL with cover-4 Recessed soil-thiocoumarin function of mol/L
Hybrid material aqueous solution；
Take configured 1 × 10-3The Hg of mol/L2+Solion be diluted to 1 × 10 respectively-6mol/L、2×10-6mol/L、5
×10-6mol/L、7×10-6mol/L、1×10-5mol/L、2×10-5mol/L、5×10-5mol/L、1×10-4mol/L、5×
10-4The solution of mol/L；
The 1 × 10 of 2 mL is taken respectively-6mol/L、2×10-6mol/L、5×10-6mol/L、7×10-6mol/L、1×10-5mol/
L、2×10-5mol/L、5×10-5mol/L、1×10-4mol/L、5×10-4mol/L、1×10-3The Hg of mol/L2+Solion
It is added to 11 and is equipped with the 1 × 10 of 5mL-4 In the recessed soil of mol/L-thiocoumarin function hybrid material aqueous solution reagent bottle
10 in, cover tightly bottle cap, stood after concussion, observation stand 5min, 30min, 1h, 5h when 11 reagent bottles in liquid face
Color photographs to record, as shown in figure 3, the Hg being added from left to right in figure2+Concentration is respectively 0 mol/L, 1 × 10-6mol/L、2×
10-6mol/L、5×10-6mol/L、7×10-6mol/L、1×10-5mol/L、2×10-5mol/L、5×10-5mol/L、1×10- 4mol/L、5×10-4mol/L、1×10-3mol/L。
As can be drawn from Figure 3, ion concentration of mercury is 5 × 10-5When mol/L or more, recessed soil matrix thiocoumarin dye colour
Variation is obvious, shows bright yellow in water.And ion concentration of mercury is higher, and color change is more obvious.Therefore this is miscellaneous
Change material to be expected to only to judge the ingredient for whether having mercury ion in water outlet by naked eye identification.But for the mercury of extremely low concentration
Ion only is also difficult to find out to distinguish with visually observing, it is also necessary to which other auxiliary detection means are proved.
Embodiment 7: ultraviolet-visible spectrum analysis
Respectively survey thiocoumarin, reacted with mercury ion after cumarin, recessed soil matrix thiocoumarin hybrid material and mercury from
The ultraviolet-visible spectrogram of recessed soil matrix cumarin after son reaction, as shown in Figure 4.
As can be drawn from Figure 4, thiocoumarin has a major absorbance peak, the dye after reacting with mercury ion at 520 nm
Oxidation reaction occurs for material, generates oxo cumarin, and blue shift occurs for characteristic absorption peak, is 465 nm.Recessed soil matrix hydridization dyestuff with
Characteristic absorption peak after mercury ion reaction obviously weakens, but there is no displacements for peak value.The sulphur research shows that hydridization does not have an impact
For the structure of cumarin molecule, and hybrid material still has the specific selectivity of former dyestuff.
Claims (10)
1. recessed soil-thiocoumarin function hybrid material, which is characterized in that it is by molecular dimension and recessed native duct size phase
The thiocoumarin fluorescent dye matched, hydridization is prepared under certain condition with recessed soil；
The structural formula of the thiocoumarin are as follows:
。
2. recessed soil-thiocoumarin function hybrid material preparation method, which comprises the steps of:
Recessed soil pretreatment:
Raw ore is rolled, grinds recessed soil after crossing 200 meshes, is ground 5 ~ 10 minutes, be added in recessed soil deionized water mashing, from
The non-clay impurity of lower layer is removed after the heart, mashing and centrifugally operated 3 ~ 4 times in repetitions；By gained paste body shape after above-mentioned mashing and centrifugation
Recessed soil is put into refrigerator freezing 6 ~ 7 hours, takes out and thaws, and the recessed earth sample twin rollers after defrosting squeeze roller 5 ~ 6 times, scrape
To the sample after roller and isopropanol solvent displacement is carried out, obtains pretreated recessed soil；
Wet process hydridization:
It takes pretreated recessed soil to mix with thiocoumarin dyestuff, isopropanol is added, high speed is beaten, and is configured to slurry, is stirred
Afterwards；Above-mentioned slurry is placed in ultrasonic wave after shaking, is dried in drying box, takes out grinding, then be placed in a vacuum drying oven height
Temperature bakes；Sample after baking is eluted loose thiocoumarin postposition with solvent to dry in a vacuum drying oven, is obtained recessed
Soil-thiocoumarin function hybrid material after vacuumizing, is passed through inert gas preservation.
3. the preparation method of recessed soil-thiocoumarin function hybrid material according to claim 2, it is characterised in that: institute
State isopropanol solvent displacement step are as follows: in isopropanol, supernatant will be abandoned after high speed mashing, high speed centrifugation to the sample dispersion after roller
Liquid obtains lotion, repeats isopropanol solvent and replaces 2 ~ 3 times, obtains pretreated recessed soil；The beating rate is 8000 ~ 12000
Rpm, beating time are 10 ~ 30min；Centrifugal speed is 2500 ~ 3500 rpm, and centrifugation time is 20 ~ 40min.
4. the preparation method of recessed soil-thiocoumarin function hybrid material according to claim 2, it is characterised in that: institute
It states in recessed native pre-treatment step, beating rate is 8000 ~ 12000 rpm, and beating time is 20 ~ 40min；Centrifugal speed is 3000
~ 4000 rpm, centrifugation time are 20 ~ 40min.
5. the preparation method of recessed soil-thiocoumarin function hybrid material according to claim 2, it is characterised in that: institute
It states in wet process hybridisation step, the mass ratio of pretreated recessed soil and thiocoumarin dyestuff is 20 ~ 30:1.
6. the preparation method of recessed soil-thiocoumarin function hybrid material according to claim 2, it is characterised in that: institute
The solid content for stating slurry in wet process hybridisation step is 1 ~ 3wt%.
7. the preparation method of recessed soil-thiocoumarin function hybrid material according to claim 2, it is characterised in that: institute
Stating drying temperature in wet process hybridisation step is 60 DEG C ~ 80 DEG C, and drying time is 4 ~ 6h；Stoving temperature is 100 DEG C ~ 140 DEG C, is baked
Time is 40 ~ 60h.
8. the preparation method of recessed soil-thiocoumarin function hybrid material according to claim 2, it is characterised in that: institute
State the step of solvent elutes in wet process hybridisation step are as follows: the sample after baking is placed in solvent, high speed centrifugation, after centrifugation
Take out upper layer liquids recovery, lower sediment thing it is dry recessed soil-thiocoumarin function hybrid material；The centrifugal rotational speed is
6000 ~ 10000 rpm, centrifugation time are 20 ~ 40min, and the drying carries out in a vacuum drying oven, and drying temperature is 20 ~ 40
DEG C, drying time is 8 ~ 14h.
9. the preparation method of recessed soil-thiocoumarin function hybrid material according to claim 2, it is characterised in that: institute
Stating eluting solvent in wet process hybridisation step is methylene chloride or isopropanol or both mixing.
10. the application of recessed soil-thiocoumarin function hybrid material, which is characterized in that the function hybrid material is used for mercury ion
Detection.
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